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Micro and Nano-Characterization of Zn-Clays in Nonsulfide Supergene Ores of Southern Peru

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Micro and Nano-Characterization of Zn-Clays in Nonsulfide Supergene Ores of Southern Peru American Mineralogist, Volume 100, pages 2484–2496, 2015 Micro- and nano-characterization of Zn-clays in nonsulfide supergene ores of southern Peru NICOLA MONDILLO1,*, FERNANDO NIETO2 AND GIUSEPPINA BALASSONE1 1Dipartimento di Scienze della Terra, dell’Ambiente e delle Risorse, Università degli Studi di Napoli Federico II, Via Mezzocannone, 8 I-80134 Napoli Italy 2Departamento de Mineralogía y Petrología and IACT, Universidad de Granada, CSIC, Av. Fuentenueva, 18002 Granada, Spain ABSTRACT Zn-clays are associated with several supergene nonsulfide ore deposits worldwide, where they are either the prevailing economic minerals, or minor components of the weathering-derived mineral assemblage. A TEM-HRTEM study on Zn-clays from nonsulfide ore deposits of Accha and Yanque (Peru) was carried out, to properly determine the chemistry and complex texture of these clays, not fully defined in other previous works on these (but also on other similar) deposits. The Zn-clays oc- curring at Accha and Yanque are constituted by a mixture of sauconite and Zn-bearing beidellite. The chemical composition of sauconite varies in a range of values, without any chemical gap, around the average composition: Ca0.15K0.05(Zn2.1Mg0.2Al0.4Fe0.15Mn0.02)(Si3.5Al0.5)O10(OH)2·nH2O. Beidellites present an average composition close to stoichiometry with the addition of Zn: Ca0.05K0.15(Al1.6Zn0.25Mg0.1Fe0.15)(Si3.6Al0.4)O10(OH)2·nH2O. The chemical composition of both sauconite and beidellite is consistent through the samples, with sauconite affected by a wider variation in composition than beidellite. The textures of Zn-bearing smec- tites clearly indicate that a part of these clays grew on precursory mica-like phyllosilicates, whereas another part was derived from a direct precipitation from solutions. The occurrence of a paragenesis with trioctahedral and dioctahedral smectites demonstrates that, as observed in other environments, also in a Zn-bearing system both smectite types are stable. As proved for other analogous trioctahedral- dioctahedral smectite systems (e.g., saponite-beidellite), also in the sauconite-beidellite system a chemical compositional gap exists within the series. The texture indicating a direct precipitation from solutions does not exclude that a smectite amount could be genetically related to hydrothermal fluids, even if several other characteristics (e.g., the paragenetical association with Fe-hydroxides typical of gossans) confirm the supergene origin for the bulk of the deposit. Keywords: Sauconite, Zn-beidellite, nonsulfide zinc ore deposits, TEM-HRTEM INTRODUCTION minerals or minor components of the weathering-derived mineral Zn-bearing clay minerals occur in several nonsulfide zinc assemblage (Balassone et al. 2008; Boland et al. 2003; Boni et ores (Hitzman et al. 2003; Large 2001). Zinc nonsulfide deposits al. 2009; Borg et al. 2003; Coppola et al. 2008; Emselle et al. are concentrations of economic Zn-oxidized minerals, mainly 2005; Frondel 1972; Ahn 2010; Kärner 2006). The best example represented by smithsonite, hydrozincite, hemimorphite, sau- is the world-class Skorpion mineralization (Namibia)—the conite, and willemite, markedly different from sphalerite ores, largest supergene nonsulfide zinc deposit in the world (original typically exploited for zinc (Hitzman et al. 2003; Large 2001). reserves of 24.6 Mt ore at 10.6% Zn)—where sauconite, the Nonsulfide ores are genetically related to supergene or hypogene trioctahedral Zn-bearing smectite (Newman and Brown 1987; processes: the supergene deposits primarily form from the oxida- Ross 1946), predominates over the other Zn-oxidized minerals tion of sulfide-bearing concentrations in a weathering regime, (Borg et al. 2003; Kärner 2006). whereas the hypogene deposits form after mineral precipitation Herein we present the first combined TEM-AEM and HRTEM from hydrothermal or metamorphic fluids (Hitzman et al. 2003). crystal-chemical characterization of natural Zn-clay minerals, Zn-clays are worldwide associated with several supergene associated with two nonsulfide ore deposits in Peru (Yanque and nonsulfide ores, where they are either the prevailing economic Accha). In fact, TEM is pivotal for the characterization of crys- talline materials at nano- and sub-nanometer scale, such as clays (Nieto and Livi 2013), allowing for a wide range of imaging and * E-mail: [email protected] diffraction techniques. When coupled with AEM analytical tools, 0003-004X/15/1112–2484$05.00/DOI: http://dx.doi.org/10.2138/am-2015-5273 2484 MONDILLO ET AL.: MICRO- AND NANO-CHARACTERIZATION OF Zn-CLAYS 2485 FIGURE 1. (a) General geologic map of the Andahuaylas-Yauri metallogenic province (modified from Perelló et al. 2003). (b) Geologic map of the Yanque deposit area (modified from Mondillo et al. 2014a). c( ) Geologic map of the Accha deposit area (modified from Boni et al. 2009). TABLE 1. Zn-bearing clay minerals and other phyllosilicates elemental composition and atomic structure down to a single atom Name Ideal formulaa 2+ can be provided as well. The aim of this work is to determine Baileychlore (Zn,Fe ,Al,Mg)6(Si,Al)4O10(OH)8 2+ 2+ Bannisterite KCa(Mn ,Fe ,Zn,Mg)20(Si,Al)32O76(OH)16·4–12H2O chemistry and textures of the Zn-clays occurring in the Yanque Fraipontite (Zn,Al)3(Si,Al)2O5(OH)4 and Accha deposits. These characteristics can be important when 3+ 3+ 2+ Franklinfurnaceite Ca2(Fe ,Al)Mn Mn3 Zn2Si2O10(OH)8 2+ planning a correct metallurgical processing, but also, being strictly Hendricksite K(Zn,Mg,Mn )3(Si3Al)O10(OH)2 Sauconite Na0.3Zn3(Si,Al)4O10(OH)2·4H2O related to environmental conditions during mineral formation, al- a IMA accepted. low to better constrain the genesis of the ore deposits. 2486 MONDILLO ET AL.: MICRO- AND NANO-CHARACTERIZATION OF Zn-CLAYS TABLE 2. XRD semi-quantitative analyses of Yanque and Accha samples selected for TEM study, after Boni et al. (2009) and Mondillo et al. (2014) Drillcore Latitude Longitude Drillhole Sample depth from the Sample Hemimorphite Smithsonite Zn-smectite (Y)a (X)a elevation (m.s.l.) top of the core (m) name YA-01 8430548 815103 3562 1.5 YA-A O OO OOO YA-02 8430449 815202 3566 5.0 YA-B OOO – OOO YA-05 8430484 815297 3549 8.5 YA-C OO – OOO YA-13 8430673 815099 3544 9.0 YA-D OO – OOO YA-20 8430461 815295 3553 9.0 YA-E – – OOOO MET1-26 8453672 186758 4287 98.5 ACC – O OOOO a Coordinates: UTM, zone: 18L (Yanque) and 19L (Accha), datum: WGS84; – = not found, O <5 wt%, OO 5–20 wt%, OOO 20–40 wt%, OOOO 40–60 wt%. (Table extends on next page) AN OVERVIEW ON ZN-BEARING PHYLLOSILICATES Fraipontite is considered a weathering-related clay mineral, as, A list of Zn-bearing clay minerals and other phyllosilicates is for example, in the Belgian deposits (Coppola et al. 2008), or given in Table 1. Sauconite is the predominant Zn-bearing clay also associated with low-temperature hydrothermal fluids, as in in zinciferous nonsulfide ore deposits (Boni 2005; Hitzman et al. Preguiça mine, Southern Portugal (Will et al. 2014). 2003). It was recognized for the first time in the Uberroth Mine, Baileychlore, the Zn-bearing end-member of the trioctahe- near Friendensville, in the Saucon Valley of Pennsylvania (Genth dral chlorite series, was recognized and validated by Rule and 1875). The validity of the species was later proved by Ross Radke (1988) in a specimen from the Red Dome deposit, North (1946), who also produced the chemical formula still accepted Queensland (Australia). by the International Mineralogical Association (IMA). Sauconite A Zn-phyllosilicate intermediate between chlorite and mica has a saponite-like structure, with a tetrahedral charge related to is the franklinfurnaceite (Peacor et al. 1988), which was solely Al/Si substitutions in tetrahedral sheets (Faust 1951; Ross 1946), recognized in association with willemite in the Franklin mine, while Zn takes the place of Mg in the octahedral positions. New Jersey (U.S.A.). Several experimental studies on the synthesis and stability Up to date, in clearly hydrothermal/metamorphic depos- of sauconite were carried out (Harder 1977; Higashi et al. 2002; its in the U.S.A. (e.g., Franklin, New Jersey) and Australia Kloprogge et al. 1999; Pascua et al. 2010; Petit et al. 2008; Roy (Broken Hill), two types of Zn-mica have been identified, i.e., and Mumpton 1956; Tiller and Pickering 1974). These studies bannisterite (Heaney et al. 1992) and hendricksite (Robert and demonstrated that Zn-smectite can precipitate from solutions of Gaspérin 1985). silicic acid, variously mixed with Zn-compounds (Zn-chloride, Zn-oxide, or Zn-hydroxide), Na-compounds, and Al-compounds, BACKGROUND INFORMATION ON PERUVIAN ZN at temperatures ranging between 20 and 200 °C for pH from 6 to CLAY-BEARING DEPOSITS 12. The retention of base (Zn) and heavy metals in other phyl- losilicate lattices through adsorption mechanisms, as in kaolinite, Geological setting has been also investigated (Gu and Evans 2008; Miranda-Trevino The present study is based on the Zn-smectites from the and Coles 2003; Srivastava et al. 2005). Yanque and Accha nonsulfide Zn-Pb deposits, Cuzco region, in Several occurrences of sauconite have been reported world- southern Peru (Boni et al. 2009; Mondillo et al. 2014a). wide, e.g., in the Moresnet-Altenberg nonsulfide deposit (La The Yanque and Accha deposits are located in the Calamine) in Belgium (Coppola et al. 2008; Frondel 1972), in Andahuaylas-Yauri metallogenic province, extending for sev- the supergene weathering zones of the Irish Tynagh and Sil- eral hundred square kilometers around the town of Cuzco. The vermines deposits (Balassone et al. 2008), in the Shaimerden Andahuaylas-Yauri province hosts numerous porphyry copper deposit, Kazakhstan (Boland et al. 2003), in the Sierra Mojada and porphyry-related skarn deposits that are spatially and tem- Zn district in Mexico (Ahn 2010), and in the Reliance deposit porally associated with the middle Eocene to early Oligocene near Beltana, South Australia (Emselle et al.
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